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WO2024116971A1 - Cellule électrochimique et cellule électrochimique avec séparateur - Google Patents

Cellule électrochimique et cellule électrochimique avec séparateur Download PDF

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Publication number
WO2024116971A1
WO2024116971A1 PCT/JP2023/041813 JP2023041813W WO2024116971A1 WO 2024116971 A1 WO2024116971 A1 WO 2024116971A1 JP 2023041813 W JP2023041813 W JP 2023041813W WO 2024116971 A1 WO2024116971 A1 WO 2024116971A1
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WO
WIPO (PCT)
Prior art keywords
layer
current collecting
hydrogen electrode
electrochemical cell
frame
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/041813
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English (en)
Japanese (ja)
Inventor
一博 水木
至貢 岩崎
直哉 秋山
正幸 新海
真司 藤崎
誠 大森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP2024561413A priority Critical patent/JPWO2024116971A1/ja
Priority to DE112023004955.6T priority patent/DE112023004955T5/de
Publication of WO2024116971A1 publication Critical patent/WO2024116971A1/fr
Priority to US19/198,710 priority patent/US20250266471A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material

Definitions

  • the present invention relates to an electrochemical cell and an electrochemical cell with a separator.
  • electrochemical cells electrolysis cells, fuel cells, etc.
  • electrolyte layer disposed between a first electrode layer and a second electrode layer
  • the electrochemical cell divides the space on the first electrode layer side from the space on the second electrode layer side, and is joined to a metal separator that is electrically connected to the first electrode layer.
  • the objective of the present invention is to provide an electrochemical cell and an electrochemical cell with a separator that can improve gas supply efficiency.
  • the electrochemical cell according to the first aspect of the present invention comprises a current collecting layer, a gas sealing layer surrounding the lateral periphery of the current collecting layer, a frame surrounding the lateral periphery of the gas sealing layer, a first electrode layer disposed on the current collecting layer, an electrolyte layer disposed on the first electrode layer, and a second electrode layer disposed on the opposite side of the first electrode layer with respect to the electrolyte layer.
  • the electrochemical cell according to the second aspect of the present invention is the electrochemical cell according to the first aspect, in which the porosity of the gas sealing layer is 5% or less.
  • the electrochemical cell according to the third aspect of the present invention is the electrochemical cell according to the first or second aspect, and the gas sealing layer includes a first constituent element contained in the current collecting layer and a second constituent element contained in the frame.
  • the electrochemical cell according to the fourth aspect of the present invention is the electrochemical cell according to the third aspect, in which the gas sealing layer includes a composite oxide containing a first constituent element and a second constituent element.
  • the electrochemical cell according to the fifth aspect of the present invention is the electrochemical cell according to any one of the first to fourth aspects, in which the thermal expansion coefficient of the gas sealing layer is between the thermal expansion coefficient of the current collecting layer and the thermal expansion coefficient of the frame body.
  • the electrochemical cell according to the sixth aspect of the present invention is the electrochemical cell according to any one of the first to fifth aspects, and the frame has insulating properties.
  • the electrochemical cell according to the seventh aspect of the present invention is the electrochemical cell according to any one of the first to sixth aspects, in which the porosity of the frame is 15% or less.
  • the electrochemical cell according to the eighth aspect of the present invention is the electrochemical cell according to any one of the first to seventh aspects, in which the thickness of the current collecting layer is greater than the thickness of each of the first electrode layer, the electrolyte layer, and the second electrode layer.
  • the electrochemical cell with separator according to the ninth aspect of the present invention comprises an electrochemical cell according to any one of the first to eighth aspects, a metal separator electrically connected to the current collecting layer, and a sealing portion that seals the gap between the electrolyte layer and the metal separator.
  • the present invention provides an electrochemical cell and an electrochemical cell with a separator that can improve gas supply efficiency.
  • FIG. 1 is a cross-sectional view of a separator-equipped electrolytic cell according to a first embodiment.
  • FIG. 2 is a perspective view of a frame according to the first embodiment.
  • FIG. 3 is a cross-sectional view of a separator-equipped electrolytic cell according to Modification 2.
  • FIG. 4 is a cross-sectional view of a separator-equipped electrolytic cell according to the second modification.
  • FIG. 1 is a cross-sectional view of an electrolytic cell 1 with a separator according to an embodiment.
  • the electrolytic cell 1 with a separator is an example of an "electrochemical cell with a separator" according to the present invention.
  • the separator-equipped electrolytic cell 1 comprises an electrolytic cell 10, a metallic separator 20, a current collecting member 25, and a sealing portion 30.
  • the electrolytic cell 10 is an example of an "electrochemical cell” according to the present invention.
  • a cell stack (not shown) can be formed by stacking multiple separator-equipped electrolytic cells 1 in the Z-axis direction perpendicular to the X-axis direction and the Y-axis direction.
  • the electrolysis cell 10 has a hydrogen electrode current collecting layer 11, a gas sealing layer 12, a frame 13, a hydrogen electrode active layer 14, an electrolyte layer 15, a reaction prevention layer 16, and an oxygen electrode layer 17.
  • the hydrogen electrode current collecting layer 11 is an example of a "current collecting layer” according to the present invention.
  • the hydrogen electrode active layer 14 is an example of a "first electrode layer” according to the present invention.
  • the oxygen electrode layer 17 is an example of a "second electrode layer” according to the present invention.
  • the hydrogen electrode current collecting layer 11, hydrogen electrode active layer 14, electrolyte layer 15, reaction prevention layer 16, and oxygen electrode layer 17 are stacked in this order in the Z-axis direction.
  • the hydrogen electrode current collecting layer 11, frame 13, hydrogen electrode active layer 14, electrolyte layer 15, and oxygen electrode layer 17 are required components, while the reaction prevention layer 16 is optional.
  • the hydrogen electrode current collecting layer 11 is formed in a plate shape.
  • the hydrogen electrode current collecting layer 11 has a main surface 11a and a side surface 11b.
  • the main surface 11a faces the metal separator 20.
  • the side surface 11b is continuous with the main surface 11a.
  • the side surface 11b is covered with the gas sealing layer 12.
  • the side surface 11b is approximately perpendicular to the main surface 11a, but may be inclined inward or outward with respect to the main surface 11a.
  • the hydrogen electrode current collecting layer 11 is electrically connected to the metal separator 20 via the current collecting member 25.
  • a hydrogen electrode side space S1 is formed between the hydrogen electrode current collecting layer 11 and the metal separator 20.
  • the hydrogen electrode current collecting layer 11 has a gas diffusion function that diffuses the raw material gas supplied to the hydrogen electrode side space S1 toward the hydrogen electrode active layer 14.
  • the hydrogen electrode current collecting layer 11 is a porous body having electronic conductivity.
  • the hydrogen electrode current collecting layer 11 contains nickel (Ni).
  • Ni functions as an electronic conductor and also functions as a thermal catalyst that promotes a thermal reaction between H 2 generated in the hydrogen electrode active layer 14 and CO 2 contained in the raw material gas to maintain a gas composition suitable for methanation, Fischer-Tropsch (FT) synthesis, etc.
  • the Ni contained in the hydrogen electrode current collecting layer 11 is basically present in the form of metallic Ni during operation of the electrolysis cell 10, but may also be partially present in the form of nickel oxide (NiO).
  • the hydrogen electrode current collecting layer 11 contains a ceramic in addition to nickel (Ni).
  • the ceramic may have ion conductivity.
  • examples of the ceramic that can be used include yttria (Y 2 O 3 ), magnesia (MgO), iron oxide (Fe 2 O 3 ), zirconia (ZrO 2 , including partially stabilized zirconia), yttria stabilized zirconia (YSZ), calcia stabilized zirconia (CSZ), scandia stabilized zirconia (ScSZ), gadolinium doped ceria (GDC), samarium doped ceria (SDC), and a mixed material of two or more of these.
  • the porosity of the hydrogen electrode current collecting layer 11 is not particularly limited, but can be, for example, 20% or more and 40% or less.
  • the thickness of the hydrogen electrode current collecting layer 11 is not particularly limited, but can be, for example, 150 ⁇ m or more and 1500 ⁇ m or less.
  • the hydrogen electrode current collecting layer 11 functions as a support for the electrolysis cell 10 together with the gas sealing layer 12 and the frame 13. In the Z-axis direction, the thickness of the hydrogen electrode current collecting layer 11 may be greater than the thicknesses of the hydrogen electrode active layer 14, the electrolyte layer 15, the reaction prevention layer 16, and the oxygen electrode layer 17.
  • the electrolysis cell 10 according to this embodiment is a so-called anode-supported cell. However, the electrolysis cell 10 may also be a so-called electrolyte-supported cell or a so-called cathode-supported cell.
  • the method for forming the hydrogen electrode current collecting layer 11 is not particularly limited, and tape casting, screen printing, casting, dry pressing, etc. can be used.
  • [Gas sealing layer 12] 2 is a perspective view of the gas sealing layer 12 surrounding the side periphery of the hydrogen electrode current collecting layer 11.
  • the gas sealing layer 12 surrounds the side periphery of the hydrogen electrode current collecting layer 11.
  • the side periphery of the hydrogen electrode current collecting layer 11 means the periphery of the side surface 11b.
  • the gas sealing layer 12 functions as a support for the electrolysis cell 10 together with the hydrogen electrode current collecting layer 11 and the frame 13.
  • the gas sealing layer 12 covers the side surface 11b of the hydrogen electrode current collecting layer 11. It is preferable that the gas sealing layer 12 covers the entire side surface 11b of the hydrogen electrode current collecting layer 11, but it is sufficient that the gas sealing layer 12 covers at least a portion of the side surface 11b of the hydrogen electrode current collecting layer 11.
  • the planar shape of the gas sealing layer 12 is rectangular, but it may be circular, elliptical, or polygonal with three or more sides depending on the planar shape of the hydrogen electrode current collecting layer 11.
  • the gas sealing layer 12 is a dense body having gas sealing properties. Therefore, the raw gas flowing from the hydrogen electrode side space S1 into the hydrogen electrode current collecting layer 11 can be prevented from returning to the hydrogen electrode side space S1 from the side surface 11b of the hydrogen electrode current collecting layer 11. This improves the efficiency of gas supply from the hydrogen electrode current collecting layer 11 to the hydrogen electrode active layer 14.
  • the bonding area between the gas sealing layer 12 and the hydrogen electrode current collecting layer 11 and the frame 13 can be increased, thereby improving the bonding between the gas sealing layer 12 and the hydrogen electrode current collecting layer 11 and the frame 13. From these viewpoints, the porosity of the gas sealing layer 12 is preferably 5% or less, and more preferably 2% or less.
  • the gas sealing layer 12 preferably contains a first constituent element contained in the hydrogen electrode current collecting layer 11 and a second constituent element contained in the frame 13. This can further improve the bonding between the gas sealing layer 12 and the hydrogen electrode current collecting layer 11 and between the gas sealing layer 12 and the frame 13.
  • the gas sealing layer 12 may contain a composite oxide containing a first constituent element and a second constituent element.
  • the reaction progress during sintering due to the eutectic point is promoted, and a stronger interface is formed.
  • the thermal expansion coefficient of the gas sealing layer 12 is preferably a value between the thermal expansion coefficient of the hydrogen electrode current collecting layer 11 and the thermal expansion coefficient of the frame 13. This allows the thermal stress caused by the difference in the thermal expansion coefficient between the hydrogen electrode current collecting layer 11 and the frame 13 during operation of the electrolysis cell 10a to be alleviated in the gas sealing layer 12, thereby further improving the bonding between the gas sealing layer 12 and the hydrogen electrode current collecting layer 11 and the frame 13.
  • the gas sealing layer 12 can be composed of, for example, nickel (Ni), nickel oxide (NiO), yttria (Y 2 O 3 ), magnesia (MgO), iron oxide (Fe 2 O 3 ), zirconia (ZrO 2 , including partially stabilized zirconia), alumina (Al 2 O 3 ), calcia (CaO), silica (Si 2 O 3 ), spinel (MgAl 2 O 4 , NiAl 2 O 4 ), YAG (Y 3 Al 5 O 12 ), YAM (Y 4 Al 2 O 9 ), nickel oxide-magnesia solid solution (Mg x Ni (1-x) O[0 ⁇ x ⁇ 1]), and a mixed material of two or more of these.
  • the method for forming the gas sealing layer 12 is not particularly limited, and tape casting, screen printing, casting, dry pressing, etc. can be used.
  • the frame 13 is placed on the metal separator 20.
  • the frame 13 is positioned with respect to the metal separator 20 by the sealing portion 30.
  • the frame 13 is formed in a frame shape. As shown in Figures 1 and 2, the frame 13 surrounds the side periphery of the gas sealing layer 12. In this embodiment, the frame 13 functions as a support for the electrolysis cell 10 together with the hydrogen electrode current collecting layer 11 and the gas sealing layer 12.
  • planar shape of the frame 13 is rectangular, but it may be circular, elliptical, or polygonal with three or more sides depending on the planar shapes of the hydrogen electrode current collecting layer 11 and the gas sealing layer 12.
  • the frame 13 can be made of, for example, forsterite (Mg 2 SiO 4 ), magnesium silicate (MgSiO 3 ), zirconia (including ZrO 2 and partially stabilized zirconia), magnesia (MgO), spinel (MgAl 2 O 4 , NiAl 2 O 4 ), yttria stabilized zirconia (YSZ), calcia stabilized zirconia (CSZ), nickel (Ni), nickel oxide (NiO), alumina (Al 2 O 3 ), nickel oxide-magnesia solid solution (Mg x Ni (1-x) O[0 ⁇ x ⁇ 1]), and a mixed material of two or more of these.
  • forsterite Mg 2 SiO 4
  • zirconia including ZrO 2 and partially stabilized zirconia
  • magnesia MgO
  • spinel MgAl 2 O 4 , NiAl 2 O 4
  • YSZ y
  • the frame 13 preferably has electronic insulation properties. This can prevent short circuits from occurring between the hydrogen electrode current collecting layer 11 and the metal separator 20. Therefore, there is no need to provide a short circuit prevention function to the sealing section 30 described below, and the configuration of the sealing section 30 can be simplified. This allows the electrolytic cell 10 to be easily insulated from the metal separator 20.
  • the electronic conductivity of the frame 13 is not particularly limited as long as it is sufficiently low, but can be 0.1 S/m or less.
  • the porosity of the frame 13 is not particularly limited, but can be, for example, 0.1% to 15%.
  • the porosity of the frame 13 is preferably 5% or less. This provides gas sealing properties to the frame 13 in addition to the gas sealing layer 12, thereby further preventing the raw material gas that has flowed from the hydrogen electrode side space S1 into the hydrogen electrode current collecting layer 11 from passing through the frame 13 and returning to the hydrogen electrode side space S1.
  • the width of the frame 13 in the X-axis direction is not particularly limited, but can be, for example, 0.5 mm or more and 10 mm or less.
  • the method for forming the frame 13 is not particularly limited, and tape casting, screen printing, casting, dry pressing, etc. can be used.
  • the hydrogen electrode active layer 14 functions as a cathode.
  • the hydrogen electrode active layer 14 is disposed on the hydrogen electrode current collecting layer 11.
  • the hydrogen electrode active layer 14 is covered with an electrolyte layer 15.
  • a source gas is supplied to the hydrogen electrode active layer 14 through the hydrogen electrode current collecting layer 11.
  • the source gas contains at least H2O .
  • the hydrogen electrode active layer 14 produces H 2 from the source gas in accordance with the electrochemical reaction of water electrolysis shown in the following formula (1).
  • Hydrogen electrode active layer 14 H2O+2e- ⁇ H2+O2- (1)
  • the hydrogen electrode active layer 14 When the source gas contains CO 2 in addition to H 2 O, the hydrogen electrode active layer 14 produces H 2 , CO, and O 2 ⁇ from the source gas in accordance with the co-electrochemical reactions shown in the following formulas (2), (3), and ( 4 ).
  • Hydrogen electrode active layer 14 CO 2 + H 2 O + 4e ⁇ ⁇ CO + H 2 + 2O 2 ⁇ (2)
  • Electrochemical reaction of CO2 CO2 + 2e- ⁇ CO + O2 -... (4)
  • the hydrogen electrode active layer 14 is a porous body having electronic conductivity.
  • the hydrogen electrode active layer 14 may have ion conductivity.
  • the hydrogen electrode active layer 14 may be composed of, for example, YSZ, CSZ, ScSZ, GDC, (SDC), (La, Sr) (Cr, Mn) O 3 , (La, Sr) TiO 3 , Sr 2 (Fe, Mo) 2 O 6 , (La, Sr) VO 3 , (La, Sr) FeO 3 , a mixed material of two or more of these, or a composite of one or more of these and NiO.
  • the porosity of the hydrogen electrode active layer 14 is not particularly limited, but can be, for example, 20% to 40%.
  • the thickness of the hydrogen electrode active layer 14 is not particularly limited, but can be, for example, 5 ⁇ m to 10 ⁇ m.
  • the method for forming the hydrogen electrode active layer 14 is not particularly limited, and tape casting, screen printing, casting, dry pressing, etc. can be used.
  • the electrolyte layer 15 is disposed between the hydrogen electrode active layer 14 and the oxygen electrode layer 17.
  • the reaction prevention layer 16 is disposed between the electrolyte layer 15 and the oxygen electrode layer 17, so that the electrolyte layer 15 is disposed between the hydrogen electrode active layer 14 and the reaction prevention layer 16 and is connected to both the hydrogen electrode active layer 14 and the reaction prevention layer 16.
  • the electrolyte layer 15 covers the hydrogen electrode active layer 14. As shown in FIG. 1, it is preferable that the electrolyte layer 15 covers the entire surface of the hydrogen electrode active layer 14. The outer periphery of the electrolyte layer 15 is connected to the frame 13.
  • the electrolyte layer 15 has a function of transmitting O 2- generated in the hydrogen electrode active layer 14 to the oxygen electrode layer 17.
  • the electrolyte layer 15 is a dense body that has ionic conductivity but no electronic conductivity.
  • the electrolyte layer 15 can be made of, for example, YSZ, GDC, ScSZ, SDC, lanthanum gallate (LSGM), or the like.
  • the porosity of the electrolyte layer 15 is not particularly limited, but can be, for example, 0.1% to 7%.
  • the thickness of the electrolyte layer 15 is not particularly limited, but can be, for example, 1 ⁇ m to 100 ⁇ m.
  • the method for forming the electrolyte layer 15 is not particularly limited, and tape casting, screen printing, casting, dry pressing, etc. can be used.
  • reaction prevention layer 16 The reaction prevention layer 16 is disposed between the electrolyte layer 15 and the oxygen electrode layer 17. The reaction prevention layer 16 is disposed on the opposite side of the electrolyte layer 15 to the hydrogen electrode active layer 14. The reaction prevention layer 16 prevents the constituent elements of the electrolyte layer 15 from reacting with the constituent elements of the oxygen electrode layer 17 to form a layer with high electrical resistance.
  • the reaction prevention layer 16 is made of an ion-conductive material.
  • the reaction prevention layer 16 can be made of GDC, SDC, etc.
  • the porosity of the reaction prevention layer 16 is not particularly limited, but can be, for example, 0.1% to 50%.
  • the thickness of the reaction prevention layer 16 is not particularly limited, but can be, for example, 1 ⁇ m to 50 ⁇ m.
  • the method for forming the reaction prevention layer 16 is not particularly limited, and tape casting, screen printing, casting, dry pressing, etc. can be used.
  • the oxygen electrode layer 17 functions as an anode.
  • the oxygen electrode layer 17 is disposed on the opposite side of the hydrogen electrode active layer 14 with respect to the electrolyte layer 15. In this embodiment, since the reaction prevention layer 16 is disposed between the electrolyte layer 15 and the oxygen electrode layer 17, the oxygen electrode layer 17 is connected to the reaction prevention layer 16. If the reaction prevention layer 16 is not disposed between the electrolyte layer 15 and the oxygen electrode layer 17, the oxygen electrode layer 17 is connected to the electrolyte layer 15.
  • the oxygen electrode layer 17 generates O2 from O2- transferred from the hydrogen electrode active layer 14 through the electrolyte layer 15, according to the chemical reaction of the following formula (5).
  • the O2 generated in the oxygen electrode layer 17 is released into the oxygen electrode side space S2.
  • the oxygen electrode layer 17 is a porous body having ionic and electronic conductivity, and may be made of a composite material of one or more of (La,Sr)(Co,Fe) O3 , (La,Sr) FeO3 , La(Ni,Fe) O3 , (La,Sr) CoO3 , and (Sm,Sr) CoO3 and an ion conductive material (such as GDC).
  • the porosity of the oxygen electrode layer 17 is not particularly limited, but can be, for example, 20% or more and 60% or less.
  • the thickness of the oxygen electrode layer 17 is not particularly limited, but can be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the method for forming the oxygen electrode layer 17 is not particularly limited, and tape casting, screen printing, casting, dry pressing, etc. can be used.
  • the metallic separator 20 is electrically connected to the hydrogen electrode current collecting layer 11 via the current collecting member 25.
  • the metallic separator 20 has a connection portion 20a that contacts the current collecting member 25.
  • the metallic separator 20 is made of a metallic material having electronic conductivity.
  • the metallic separator 20 can be made of an alloy material containing Cr (chromium), for example. Examples of such alloy materials include Fe-Cr alloy steel (stainless steel, etc.) and Ni-Cr alloy steel.
  • the Cr content in the metallic separator 20 is not particularly limited, but can be 4% by mass or more and 30% by mass or less.
  • the metal separator 20 may contain Ti (titanium) or Zr (zirconium).
  • the Ti content in the metal separator 20 is not particularly limited, but may be 0.01 mol% or more and 1.0 mol% or less.
  • the Al content in the metal separator 20 is not particularly limited, but may be 0.01 mol% or more and 0.4 mol% or less.
  • the metal separator 20 may contain Ti as TiO2 (titania) and may contain Zr as ZrO2 (zirconia).
  • the metallic separator 20 may have an oxide film on its surface, which is formed by oxidation of the constituent elements of the metallic separator 20.
  • a typical example of the oxide film is a chromium oxide film.
  • the chromium oxide film covers at least a portion of the surface of the metallic separator 20.
  • the current collecting member 25 electrically connects the hydrogen electrode current collecting layer 11 and the metal separator 20. As shown in Fig. 1, the current collecting member 25 is disposed in the hydrogen electrode side space S1 between the hydrogen electrode current collecting layer 11 and the metal separator 20. The current collecting member 25 contacts the main surface 11a of the hydrogen electrode current collecting layer 11 and the connection portion 20a of the metal separator 20.
  • the current collecting member 25 has electronic conductivity and breathability.
  • nickel, a nickel alloy, stainless steel, or other materials can be used as the current collecting member 25.
  • the size, shape, and position of the current collecting member 25 can be changed as appropriate.
  • the current collecting member 25 is in contact with both the hydrogen electrode current collecting layer 11 and the frame 13, but it does not have to be in contact with the frame 13.
  • the sealing portion 30 positions the frame 13 relative to the metal separator 20.
  • the sealing portion 30 is a dense body.
  • the sealing portion 30 seals the gap between the electrolytic cell 10 and the metal separator 20. This prevents gas from mixing between the hydrogen electrode side space S1 and the oxygen electrode side space S2 through the gap between the electrolytic cell 10 and the metal separator 20. Furthermore, when the frame 13 is air-permeable, the sealing portion 30 prevents gas from mixing through the frame 13 itself.
  • the sealing portion 30 is connected to the frame 13 and the electrolyte layer 15 of the electrolysis cell 10, but if the frame 13 is not breathable, the sealing portion 30 does not need to be connected to the electrolyte layer 15.
  • the sealing portion 30 preferably has electronic insulation properties. This makes it possible to more reliably prevent short circuits from occurring between the hydrogen electrode current collecting layer 11 and the metal separator 20. However, as described above, if a short circuit between the hydrogen electrode current collecting layer 11 and the metal separator 20 can be prevented by the frame 13, the short circuit prevention function of the sealing portion 30 may be auxiliary.
  • the sealing portion 30 can be made of, for example, glass, glass ceramics (crystallized glass), a composite of glass and ceramics, etc.
  • the electrolysis cell 10 includes a gas sealing layer 12 that surrounds the side periphery of the hydrogen electrode current collecting layer 11. This makes it possible to prevent the source gas that has flowed from the hydrogen electrode side space S1 into the hydrogen electrode current collecting layer 11 from returning to the hydrogen electrode side space S1 from the side surface 11b of the hydrogen electrode current collecting layer 11. This makes it possible to improve the efficiency of gas supply from the hydrogen electrode current collecting layer 11 to the hydrogen electrode active layer 14.
  • the hydrogen electrode current collecting layer 11, the gas sealing layer 12, and the frame 13 function as supports for the electrolytic cell 10, improving the strength of the electrolytic cell 10. This makes it possible to prevent the electrolytic cell 10 from being damaged by external forces applied when assembling the electrolytic cell 10 to the metal separator 20 or by thermal stresses that occur during operation of the electrolytic cell 10.
  • the hydrogen electrode current collecting layer 11 is likely to deform. However, since the hydrogen electrode current collecting layer 11 is surrounded by the gas sealing layer 12 and the frame 13, deformation of the hydrogen electrode current collecting layer 11 can be suppressed.
  • the gas sealing layer 12 surrounds only the side periphery of the hydrogen electrode current collecting layer 11 of the electrolytic cell 10, but this is not limited thereto.
  • the gas sealing layer 12 may surround the side periphery of the hydrogen electrode active layer 14 or the side periphery of the electrolyte layer 15.
  • the frame 13 is disposed on the metal separator 20, but as shown in Fig. 3, the frame 13 may be disposed on the sealing portion 30. Furthermore, if the frame 13 does not have air permeability, the sealing portion 30 may be connected to the frame 13 and not connected to the electrolyte layer 15, as shown in Fig. 4.
  • the hydrogen electrode active layer 14 functions as a cathode and the oxygen electrode layer 17 functions as an anode, but the hydrogen electrode active layer 14 may function as an anode and the oxygen electrode layer 17 may function as a cathode.
  • the constituent materials of the hydrogen electrode active layer 14 and the oxygen electrode layer 17 are switched, and a source gas is caused to flow through the outer surface of the hydrogen electrode active layer 14.
  • the hydrogen electrode current collecting layer 11 functions as an oxygen electrode current collecting layer, but the configuration and function of the oxygen electrode current collecting layer are the same as those of the hydrogen electrode current collecting layer 11 described in the above embodiment.
  • the electrolysis cell 10 has been described as an example of an electrochemical cell, but the electrochemical cell is not limited to an electrolysis cell.
  • An electrochemical cell is a general term for an element in which a pair of electrodes are arranged so that an electromotive force is generated from an overall oxidation-reduction reaction in order to convert electrical energy into chemical energy, and an element for converting chemical energy into electrical energy. Therefore, the electrochemical cell includes, for example, a fuel cell that uses oxide ions or protons as a carrier.
  • Electrolytic cell with separator 10 Electrolytic cell 11 Hydrogen electrode current collecting layer 12 Gas sealing layer 13 Frame 14 Hydrogen electrode active layer 15 Electrolyte layer 16 Reaction prevention layer 17 Oxygen electrode layer 20 Metal separator 30 Sealing portion

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Selon la présente invention, une cellule d'électrolyse (10) comprend une couche de collecteur d'électrode à hydrogène (11), une couche d'étanchéité aux gaz (12), un corps de cadre (13), une couche active d'électrode à hydrogène (14), une couche d'électrolyte (15), une couche de prévention de réaction (16) et une couche d'électrode à oxygène (17). La couche d'étanchéité aux gaz (12) entoure la périphérie latérale de la couche de collecteur d'électrode à hydrogène (11). Le corps de cadre (13) entoure la périphérie latérale de la couche d'étanchéité aux gaz (12).
PCT/JP2023/041813 2022-11-30 2023-11-21 Cellule électrochimique et cellule électrochimique avec séparateur Ceased WO2024116971A1 (fr)

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JP2024561413A JPWO2024116971A1 (fr) 2022-11-30 2023-11-21
DE112023004955.6T DE112023004955T5 (de) 2022-11-30 2023-11-21 Elektrochemische zelle und mit einem separator ausgestattete elektrochemische zelle
US19/198,710 US20250266471A1 (en) 2022-11-30 2025-05-05 Electrochemical cell and separator-equipped electrochemical cell

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JP2022-191611 2022-11-30
JP2022191611 2022-11-30

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JP2016062655A (ja) * 2014-09-12 2016-04-25 日本特殊陶業株式会社 セパレータ付燃料電池単セル
JP2019003821A (ja) * 2017-06-15 2019-01-10 トヨタ自動車株式会社 燃料電池およびその製造方法
WO2020217673A1 (fr) * 2019-04-25 2020-10-29 パナソニックＩｐマネジメント株式会社 Assemblage membrane-électrode et pile à combustible de type à oxyde solide l'utilisant

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JP3110265B2 (ja) * 1994-10-31 2000-11-20 三井造船株式会社 固体電解質型燃料電池スタックの接合材および接合方法
JP2005259490A (ja) * 2004-03-11 2005-09-22 Mitsui Eng & Shipbuild Co Ltd 固体電解質型燃料電池スタック、および固体電解質型燃料電池
US9160027B2 (en) * 2010-07-29 2015-10-13 Kyocera Corporation Fuel cell bundle and fuel cell module comprising same
JP2012091984A (ja) * 2010-10-28 2012-05-17 Mitsubishi Heavy Ind Ltd 高温シール材料、高温シール体、及び高温シール体を含む酸素透過モジュール
JP2012124020A (ja) * 2010-12-08 2012-06-28 Honda Motor Co Ltd 固体電解質燃料電池

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Publication number Priority date Publication date Assignee Title
US20050191538A1 (en) * 2000-09-09 2005-09-01 Elringklinger Ag Fuel cell unit, composite block of fuel cells and method for manufacturing a composite block of fuel cells
US20030077500A1 (en) * 2001-10-24 2003-04-24 Brian Gorbell Flat plate fuel cell stack
US20140356762A1 (en) * 2013-05-29 2014-12-04 Yong Gao Integrated Gas Diffusion Layer With Sealing Function And Method Of Making The Same
JP2016062655A (ja) * 2014-09-12 2016-04-25 日本特殊陶業株式会社 セパレータ付燃料電池単セル
JP2019003821A (ja) * 2017-06-15 2019-01-10 トヨタ自動車株式会社 燃料電池およびその製造方法
WO2020217673A1 (fr) * 2019-04-25 2020-10-29 パナソニックＩｐマネジメント株式会社 Assemblage membrane-électrode et pile à combustible de type à oxyde solide l'utilisant

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DE112023004955T5 (de) 2025-09-11
JPWO2024116971A1 (fr) 2024-06-06

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